Polyether substituted oxazolidines and the like



Patented Oct. 16, 1951 POLYETHER Sl lBS TITUTED OXAZOLIDINES AND THE LIKE Joseph .1. Games, Greenwich, Conn., assignor to v American Cyanamid Company, New York,

N. Y., a corporation of Maine No Drawing. Application July 13,1949, 7

Serial No. 104,583

12 Claims. (Cl. 260-307) The present invention tion of .2-substituted oxazolidine-polyether com- ,pe nd It is an object of this invention to prepare a -2-substituted oxazolidine .of the general formula in which X is a member of the group consisting of the radicals (CR2) aO]nH-'aI1d -(-C-H2CHOHCHO) in,

a being 1 to 4 inclusive, m being 2 to 3 inclusive,

n being 1 to 100 inclusive, B being amember of the group consisting of H and aliphatic radicals; R being amember of the group consisting of H, aliphatic, aromatic, and heterocyclic radicals; and R" being a member of the group consisting relates to the preparaof aliphatic, aromatic, an'diheterocyclic radicals.

Compounds of this formula are ;valuable as intermediates particularly in the synthesis of surface active agents, textile lubricants, and for The polyether substituted oxazolidines 'of the it present invention are, in general, water soluble and tend to hydrolyze readily in aqueous solutions.

The processfor making-the compounds-of the above formula may be described briefly as follows. A plural-carbon aldehyde or ketone such as acetaldehyde, acetone, benzaldehyde, 'isobutyraldehyde, and an alkylol amine such as ethanolamine are dissolved in a suitable solvent and reacted for a suitable period of time in anapparatus which permits stripping out the by-product water as it is formed, according to the known methods for making the oxazolidines and'oxazines. There remains dissolved in the solvent a 2-substituted oxazolidine, for example. The sol-' such as ethylene oxide, glycidol, or the like, in a suitable solvent. The epoxy compound adds at r the nitrogen atom of the oxazolidine ring, and a fairly large number of mols of epoxy compound may be so added, creating in effect a polyether side chain terminating in vhydroxyl. While up to about 100 mols of epoxy compound may be so added, the reaction proceeds faster if a smaller number, such as or less, is added. For commercial purposes 30 or 40 will frequently be found to be the optimum number of mols.

The process is not confined to the oxazolidines. The G-membered oxazine ring made by reacting propanolamine witha plur' l-carlzvon aldehyde or a ketone also condenses thyepoxy compounds of the type described'to g ydrolyzable' N-substituted polyether amine The ring maymbe formed with'almostany 'e:-commoner aldehydes or ketones. Preferenceis given to the less expensive ones purely from the viewpoint of economy; therefore, :acetone'. is preferred for the reaction. Although the two substituents on the carbonyl group of the"aldehyde or ketone are susceptible to a wide degree of variation, itis preferable to leave them fairly simple H A great varietyof epoxy compounds is available. Ethylene oxide is preferred because of "its relative cheapness, butlethylene oxide derivatives .;such as propylene oxide, glycidol, butadiene monoxidaand isobutylene oxide are also suitable. If ethylene oxide is used, the speed of reaction may be increased by employing a suitable catalyst such as trie'thylamine." The excess of epoxy compound may be varied over wide limits. Obviously,

at least one mol of epoxy compound must be used for each mol of substituted oxazolidine. No preference as to the ratio of epoxy compound to oxazolidine compound may be stated," as it is-clear that this will .dependupon the end product desired. r x

All the reactions discussed may be carried out by refluxing at atmospheric pressure, and this mode of preparationis especially preferable in making the compound ,containingthe 'oxa'z'olidine ring, in which process it is desirable to strip out water during the reaction. However, the actual condensation of the oxazolidinecompound with the epoxy compound may be carried out in an autoclave if desired. 1

The following examples illustrate the invention. While specific details .are describeiit will be understood that these examples aretgiven primarily for the purpose of illustration and that the invention in its broader aspects is not limited thereto.

PREPARATION OF OXAZOLIDINES Example 1 Z-PHENYLOXAZOLIIDINE O-cno HZNCHiCHzOH Example 2 2-ISOPROPYLOXAZOLIDINE (CHzhCHCHO H2NCHzCHzOH Cs N-CH2 By the same procedure, isobutyraldehyde 72 g. (1.0 mol) was condensed with 61 g. (1.0 mol) of ethanolamine in 250 ml. of benzene. The yield of 2-isopropyloxazolidine, a clear, colorless liquid boiling at 55-9 C./15 mm., was 91 g., 79% of theory. J

Example 3 2,2-DIMETHYL-4-ETHYLOXAZOLIDINE Acetone, 48 g. (0.83 mol), and 74 g. (0.83 mol) of 2-aminobutanol1 were condensed in 200 ml. of refluxing benzene as above. The 2,2-dimethyl- 4-ethyloxazolidine was a clear, colorless liquid boiling at 57-60 C./25 mm. The yield was 68 g., 64% of theory.

CONDENSATION or OXAZOLIDINES WITH ALKYLENE Oxmrzs Example 4 Z-PHENYLOXAZOLIDINE-l-LO MOLS ETHYLENE OXIDE 0.810s I +10CH2CH: )COH5C (C :CHzO)qCHaCHzOH oxazolidine as prepared in Example 1, and 7 g.

4 of triethylamine in 100 ml. of sec.-butyl alcohol was placed in a flask fitted with stirrer, thermometer, gas inlet tube, and cold reflux condenser. The solution was heated to 100 C. and ethylene oxide from a weighed tank was passed in at -100 C. until 297 g. (6.75 mol) had been absorbed. This required ten hours. After heating for an additional 3 hours at -105 0., refluxing had ceased.

The solvent and volatile materials were distilled ofi under water pump pressure up to C. The polyglycol substituted-2-phenyloxazolidine remaining was a dark red, viscous oil. It could not be distilled under normal conditions without decomposition.

Example 5 Z-PHENYLOXAZOLIDINE 35 MOLS ETHYLENE OXIDE CuH4CH +35CHzCH2 N C H H CsHsC N-CH: H

0-011, Co sC 7 N-CH:

((imcnoncmofi-cmononcm0H Glycidol, 30 g. (0.405 mol) was added dropwise with stirring to 15.1 g. (0.101 mol) of 2- phenyloxazolidine (as prepared in Example 1) at -160 C. The reaction was exothermic and no heating was required during the addition. The preparation was completed by heating for another hour at the same temperature. The polyglycol substituted -2-phenyloxazolidine was a dark brown viscous oil, which could not be distilled under normal conditions without decomposition.

Example 7 2-ISOPROPYLOXAZOLIDINE+2 MOLS PROPYLENE OXIDE Cg: O-GH:

GH-CH zcmcflcm -l C 1 N-CH:

CH- C 0Q, NCH:

simmers A mixture-of 29" g. :(0.25 mol) of 2-isopropyl- =oxazo1idine as pnepareddn Example ,2 and .29 g.

(0.50 mol) of propylene oxide .was placed: :a stainless .steel autoclave and .heated ,at 165 C. until the pressure had fallen to approximately 30 p. si=-i.-a-nd remained constant. The product xwas a :yellbw, viscous oil. Y

(In the last formula 3.3 means the average number of CH2CH2O- groups; that is, the compound is a mixture of polyether oxazolidines in which some of the molecules have a whole number of CH2CHO- groups greater than 3.3 and some a number less than 3.3, the statistical average being 3.3.)

Ethylene oxide was passed as in Example 1 into a solution of 32 g. (0.25 mol) of 2,2-dimethyl-4- ethyloxazolidine prepared as per Example 3, and 2.5 g. of triethylamine in 25 ml. of sec.-butyl alcohol until 55 g. (1.25 mols) of the oxide had been absorbed. This addition required 8 hours at 8599 C.

After the mixture had been heated for 3 hours at 9095 C., the solvent and volatile materials were distilled off up to 155 C. at 35 mm. pressure. Some unreacted oxazolidine distilled over at this point. The remaining polyglycol oxazolidine was a dark red viscous oil, which could not be distilled without decomposition.

While the invention has been described with particular reference to specific embodiments, it is to be understood that it is not to be limited thereto but is to be construed broadly and re stricted solely by the scope of the appended claims.

This case is a continuation-in-part of copending application, Serial No. 25,073, filed May 4, 1948.

I claim:

1. A compound of the formula in which X is a member of the'group consisting of the radicals (CR2) a] 1H and CH2CHO HCHO) 11H (1 being 1 to 4 inclusive, m being 2 to 3 inclusive, n being 1 to 100 inclusive, R being a member of the group consisting of H and aliphatic radicals; R. being a member of the group consisting of H, aliphatic and aromatic radicals; and R," being a member of the group consisting of aliphatic and aromatic radicals.

2. The compound of claim 1 in which X is L(CR2)aO]nH.

3. The compound of claim 1 in which X is (CHzCHOHCHO) 11H.

6 '1 4ivar2- phenylcxazolidine of "the :iormula.

fcmcmonfl manna-macro 40.. 35:.A tphenyloxazolidine :Qf :the .formula fi o-onf 1 ,ZCGEEQ- N-CH: dmononcnopn 6. A z-isopropyloxazolidine of the formula CHK 7. The method of making a polyether heterocyclic compound comprising heating a compound of the formula in which m is 2 to 3 inclusive, R is a member of the group consisting of H and aliphatic radicals, R is a member of the group consisting of H, aliphatic and aromatic radicals, and R." a member of the group consisting of aliphatic and aromatic radicals in the presence of an containing compound, the mol ratio of heterocyclic reactant to said CH-CH- containing' reactant being in the range 1:1 to

8. The method of making a polyether oxazolidine comprising heating an oxazolidine of the formula containing reactant being in the range 1:1 to 1:100.

9. The method according to claim 8 in'which the 1 containing compound is ethylene oxideand the REFERENCES CITED reactant molar range 15 The following references are of record in the 10. The method according to claim 9 in which me of this patent;

the axazolidine is 2-pheny1oxazo1idine.

11. The method of making a polyether oxazoli- 5 UNITED STATES PATENTS dine comprising heating 2-isopropy1oxazo1idine Number Name Date 7 with a 30-40 molar excess of ethylene oxide. 2,312,344 Logemann Mar. 2, 1943 12. The method of making a polyether oxazoli- 2,377,507 Marker June 5, 1945 dine comprising heating 2,2-dimethy1-4-ethy1ox- 2,387,830 Butz Oct. 30, 1945 azolidine with a 30-40 molar excess of ethylene 10 oxide.

JOSEPH J. CARNES. 

1. A COMPOUND OF THE FORMULA 